CN101395211A - Process for making polybutylene terephthalate (pbt) from polyethylene terephthalate (pet) - Google Patents
Process for making polybutylene terephthalate (pbt) from polyethylene terephthalate (pet) Download PDFInfo
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- CN101395211A CN101395211A CNA2007800081651A CN200780008165A CN101395211A CN 101395211 A CN101395211 A CN 101395211A CN A2007800081651 A CNA2007800081651 A CN A2007800081651A CN 200780008165 A CN200780008165 A CN 200780008165A CN 101395211 A CN101395211 A CN 101395211A
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Abstract
A composition comprising a polytrimethylene terephthalate random copolymer that (1) is derived from polyethylene terephthalate component selected from the group consisting of polyethylene terephthalate and polyethylene terephthalate copolymers and (2) contains at least one residue derived from the polyethylene terephthalate component. Methods for making such copolymers and articles made from such copolymers.
Description
The cross reference of related application
The application requires the right of priority of U.S. provisional application No.60/820447 (submission on July 26th, 2006), No.60/763093 (submission on January 27th, 2006), No.60/777901 (submission on March 1st, 2006), and the full content of above provisional application is hereby incorporated by.
Background of invention
Polyethylene terephthalate (also being known as " PET ") is the polyester of terephthalic acid and ethylene glycol, and can be by dimethyl terephthalate (DMT) and ethylene glycol, and perhaps terephthalic acid and ethylene glycol or ethylene oxide polycondensation obtain.PET is a kind of thermoplastic material that can hemihedral crystal (opaque and white) form exists that both can unsetting (transparent) form exists also.In general, it has chemical resistance to mineral oil, solvent and acid, but alkali is not had.Hemihedral crystal PET has good intensity, ductility, rigidity and hardness.Unsetting PET has better ductility, but rigidity and hardness are relatively poor.PET is used to make the bottle of soft drink, fiber and other household articles and the consumer's goods of various uses.
Unfortunately, although done the effort of reclaiming, the whole world still has billions of pounds the PET to become solid refuse and be introduced into the landfill or burned every year.The PET that is introduced into the landfill in a large number causes great waste, and the burning of PET has then destroyed this material by non-renewable hydrocarbons resource preparation, and they should be utilized more efficiently.
Known poly terephthalic acid 1, ammediol ester (also being known as " PTT " here) are to can be used for the engineering thermoplasties that injection moulding is used, and as United States Patent (USP) 5,326,806 is described.In general, PTT prepares by the following method: 1 of molar excess, ammediol and terephthalic acid at high temperature carry out polystep reaction (esterification/polycondensation), remove water byproduct, continue one section effectively preparation poly terephthalic acid 1, the time of ammediol ester.The selective polymerization condition, thus the productive target limiting viscosity at least about 0.4dl/g, preferred about molten polyester of 0.4 to about 1.0dl/g.Poly terephthalic acid 1, ammediol ester also can be by 1, ammediol and dimethyl terephthalate (DMT) prepared in reaction.
Unfortunately, traditional PTT preparation method can not satisfy and reduces the requirement that those are incinerated or buried in the pet waste of landfill usually for a long time.Prepare the big energy of PTT needs by monomer.A kind of novel method for preparing PTT by non-monomer source of expectation exploitation.The modified PTT random copolymers that exploitation is come by the preparation of PET rather than monomer, and show and derived from the suitable performance of monomeric PTT, also will be very helpful.
For the above reasons, be necessary that exploitation replaces monomer with PET, preparation poly terephthalic acid 1, the improved method of ammediol ester.
For the above reasons, be necessary to develop the novel material of derived from PET, its have with based on monomeric poly terephthalic acid 1, the performance that the ammediol ester is similar.
Summary of the invention
The present invention relates to a kind of composition, comprise poly terephthalic acid 1, ammediol ester random copolymers, this random copolymers (1) comprises at least a residue derived from the polyethylene terephthalate component derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer and (2).
In one embodiment, the present invention relates to by this composition molding or extrude the goods that make.
In another embodiment, the present invention relates to prepare the method for this based composition, it may further comprise the steps:
(a) be selected from the polyethylene terephthalate component of polyethylene terephthalate and pet copolymer by following depolymerization: with (i) polyethylene terephthalate component and (ii) 1, ammediol is under at least one atmospheric pressure, in the presence of catalyst component, and be enough to described polyethylene terephthalate component depolymerized under the inert atmosphere conditions of molten mixture and react, this molten mixture comprises the oligopolymer of poly terephthalic acid ethylene glycol, poly terephthalic acid 1, the oligopolymer of ammediol ester, the oligopolymer of blended glycol, 1, ammediol and ethylene glycol;
Wherein, in step (a) process, described polyethylene terephthalate component and 1, ammediol mixes in liquid phase, with 1, ammediol backflow Returning reactor;
(b) molten mixture is placed be lower than under the atmospheric environment, and the temperature of this molten mixture that raises, until being enough to form poly terephthalic acid 1, the temperature of ammediol ester random copolymers, this random copolymers (1) comprises at least a residue derived from the polyethylene terephthalate component derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer and (2).
In another embodiment, the present invention relates to prepare the method for this based composition, wherein this method comprises:
Be selected from the polyethylene terephthalate component of polyethylene terephthalate and pet copolymer by following depolymerization: under at least one atmospheric pressure, in the presence of catalyst component, and be enough to described polyethylene terephthalate component is depolymerized under the condition of first molten mixture, in reactor, stir polyethylene terephthalate component and ethylene glycol, this first molten mixture contains oligopolymer, the ethylene glycol that is selected from the ethylene glycol terephthalate part, and combination;
In the presence of catalyst component, in 190 ℃ to 240 ℃ temperature range, and be enough to form under the condition of second molten mixture, in first molten mixture of reactor, add 1, ammediol, this second molten mixture comprises and is selected from following component: contain the ethylene glycol terephthalate part oligopolymer, contain oligopolymer, propylene glycol, the ethylene glycol of propylene glycol ester terephthalate's part and combination thereof; With
(c) be lower than under the atmospheric condition in stirring and pressure, the temperature of second molten mixture is elevated to 240 ℃ to 260 ℃ temperature, thereby form poly terephthalic acid 1, ammediol ester random copolymers, this random copolymers (1) comprises at least a residue derived from the polyethylene terephthalate component derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer and (2).
With reference to following description and appended claims, these and other features of the present invention, character and advantage will obtain understanding better.
Detailed Description Of The Invention
The present invention is based on significant a discovery, promptly now can be from poly-(ethylene glycol terephthalate), for example the bottle of exhausted soft drink prepares the poly terephthalic acid 1 of modification, ammediol ester component.With traditional poly terephthalic acid 1, ammediol ester (derived from monomeric poly terephthalic acid 1, ammediol ester) difference, the poly terephthalic acid 1 of this modification, ammediol ester component comprises the polyethylene terephthalate residue, for example the material such as ethylene glycol and m-phthalic acid.Advantageously, although the poly terephthalic acid 1 that uses, the ammediol ester structurally is different from primary, derived from monomeric poly terephthalic acid 1, the ammediol ester, but the application's poly terephthalic acid 1, the ammediol ester show with derived from monomeric poly terephthalic acid 1, the performance that the ammediol ester is similar.
Except that operation embodiment and other had explanation, all that use in specification sheets and claims related to into the numeral of dosis refracta, reaction conditions etc. or express and all are interpreted as in all instances with " approximately " modification.The application discloses various numerical ranges.Because numerical range is a successive, so they comprise each numerical value between minimum value and the maximum value.Unless expressly stated otherwise,, the specified various numerical ranges of the application all are approximations.
All molecular weight all refer to the number-average molecular weight that recorded by polystyrene standards among the application.Ins and outs comprise following several: (i) equipment: Waters 2695 separation modules; (ii) detector: Waters2487 biabsorption Zi Waijianceqi @273 and 295 nanometer instrument and Waters410 refractometer (refractomer); (iii) moving phase: 5% HFIP95% chloroform; (iv) GPC post: Polymer LabsPL HFIP gel 250 * 4.6mm; (v) flow: 0.3ml/min; (vi) volume injected: 10 μ l; (vii) polystyrene standards: Polymer Lab ' s Easical PS-, 580-7,500,000Da.
The present invention relates to comprise poly terephthalic acid 1, the composition of ammediol ester random copolymers, this random copolymers (1) comprises at least a residue derived from the polyethylene terephthalate component derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer and (2).
Be present in modification poly terephthalic acid 1, the residue derived from the polyethylene terephthalate component in the ammediol ester component can be selected from the ethylene glycol group, diethylene glycol group, isophthalic acid group, antimony containing compounds, germanium-containing compound, titanium-containing compound, cobalt compound, sn-containing compound, 1,3-cyclohexanedimethanol isomer, 1,4-cyclohexanedimethanol isomer, 1, the 3-cyclohexane dimethanol, 1, the 4-cyclohexane dimethanol, 1,3-cyclohexanedimethanol trans-isomer(ide), 1,4-cyclohexanedimethanol trans-isomer(ide), alkali salt (alkali salt) (comprises calcium salt, magnesium salts, sodium salt and sylvite), P contained compound and negatively charged ion, sulfocompound and negatively charged ion, naphthalene dicarboxylic acids (naphthalane dicarboxylicacid), 1, ammediol group, and combination.
According to the factor such as polyethylene terephthalate and pet copolymer, residue can contain various combinations.For example in one embodiment, the mixture that comprises ethylene glycol and glycol ether derived from the residue of polyethylene terephthalate component.This mixture can also contain extra material, such as m-phthalic acid.This mixture also can contain 1,3-cyclohexane dimethanol, 1,4 cyclohexane dimethanol cis-isomeride, 1,3-cyclohexanedimethanol trans-isomer(ide), 1,4 cyclohexane dimethanol trans-isomer(ide) and combination thereof.In one embodiment, residue derived from the polyethylene terephthalate component can be selected from 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, 1,3-cyclohexanedimethanol trans-isomer(ide), 1,4 cyclohexane dimethanol trans-isomer(ide) and combination thereof.In another embodiment, residue derived from the polyethylene terephthalate component can be selected from ethylene glycol group, diethylene glycol group, isophthalic acid group, 1,3-cyclohexane dimethanol, 1,3-cyclohexanedimethanol trans-isomer(ide), 1,4-cyclohexane dimethanol, 1,4 cyclohexane dimethanol trans-isomer(ide) and combination thereof.In another embodiment, derived from the residue of polyethylene terephthalate component comprise ethylene glycol, glycol ether, contain antimony, the mixture of the compound of germanium, tin, titanium, cobalt.As mentioned above, in this mixture, at least a residue derived from the polyethylene terephthalate component also comprises isophthalic acid group.
Molar weight derived from the residue of polyethylene terephthalate component can change.In one embodiment, residue derived from the polyethylene terephthalate component is selected from ethylene glycol group, diethylene glycol group and cyclohexanedimethanol group, and content be 0.1mol% to 10mol%, be as the criterion in the glycol of 100mol% in the composition (for example moulding compound).In another embodiment, further comprising content derived from the residue of polyethylene terephthalate component is 0 to 10mol% isophthalic acid group, with poly terephthalic acid 1, and the acid functional group of the 100mol% meter that is as the criterion in the ammediol ester copolymer.The material total amount of polyethylene terephthalate residue can change.For example, sometimes the amount of mixture can arrive 2.5wt% for 1.8wt%, and perhaps 0.5wt% is to 2wt%, and perhaps 1wt% is to 4wt%.The amount of diethylene glycol group can be 0.1mol% to 10mol%, be as the criterion in the glycol of 100mol% in the moulding compound.The amount of isophthalic acid group be 0.1mol% to 10mol%, be as the criterion in the acid of 100mol% in the moulding compound.
In further describing following a kind of embodiment, poly terephthalic acid 1, ammediol ester random copolymers can be further derived from getting 1 of authigenic material, ammediol.These biomass can include but not limited to carbohydrate, for example derived from the sugar in starch or Mierocrystalline cellulose source; Cereal includes but not limited to be selected from the cereal of corn, wheat and combination thereof.These biomass comprise that also biologically deutero-and suitable zymotechnique or chemical process produce 1, other hydrocarbons of ammediol.The example of the biomass that these are suitable includes but not limited to glycerine, 3-hydroxy-propionic acid.
The application's modification poly terephthalic acid 1, ammediol ester random copolymers can be by new method preparation, PET is by depolymerization in the method, and place to make the poly terephthalic acid 1 that obtains, under the condition of ammediol ester random copolymers through the PET of depolymerization molten mixture polymerization generation modification.For example, modification poly terephthalic acid 1, ammediol ester random copolymers can prepare by the following method, comprising:
(a) be selected from the polyethylene terephthalate component of polyethylene terephthalate and pet copolymer by following depolymerization: with (i) polyethylene terephthalate component and (ii) 1, ammediol is under at least one atmospheric pressure, in the presence of catalyst component, and be enough to described polyethylene terephthalate component depolymerized under the inert atmosphere conditions of molten mixture and react, this molten mixture comprises the oligopolymer of poly terephthalic acid ethylene glycol, poly terephthalic acid 1, the oligopolymer of ammediol ester, the oligopolymer of blended glycol, 1, ammediol and ethylene glycol; In step (a) process, make described polyethylene terephthalate component and 1, ammediol mixes in liquid phase, with 1, ammediol backflow Returning reactor; (b) molten mixture is placed be lower than under the atmospheric environment, and the temperature of this molten mixture that raises, until being enough to form poly terephthalic acid 1, the temperature of ammediol ester random copolymers, this random copolymers (1) comprises at least a residue derived from the polyethylene terephthalate component derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer and (2).
Preparation modification poly terephthalic acid 1, the PET component of ammediol ester random copolymers generally comprises (waste material) PET thin slice, powder/chip or the particle of recovery.Before the use, usually PET is handled to remove impurity, as paper, tackiness agent, olefin polymer and other pollutents.In addition, this PET component can comprise PET thin slice, chip or the particle that is not refuse.The PET that can become solid refuse like this, usually obtains efficient and utilization now with being fruitful.In one embodiment, the PET component also comprises other polyester.These PET components also can comprise polyester copolymer.These examples of material comprise polyalkylene terephthalate, it can be selected from polyethylene terephthalate, poly-hexanaphthene terephthalate, terephthalate and the multipolymer that comprises the comonomer of cyclohexyl dimethanol and ethylene glycol, terephthalic acid and the multipolymer that comprises the comonomer of cyclohexyl dimethanol and ethylene glycol, poly terephthalic acid 1, the ammediol ester, poly terephthalic acid benzene dimethyl ester, poly-dianol terephthalate (polydianol terephthalate), polybutylene terephthalate, poly-naphthalate and combination thereof.
The temperature that adopts in the described method can change.For example, the polyethylene terephthalate component can be 180 ℃ to 260 ℃ temperature range depolymerization.In another embodiment, when molten mixture stood to be lower than an atmospheric pressure, the temperature of molten mixture can be elevated to 240 ℃ to 270 ℃ temperature range.
As indicated above, in some cases, poly terephthalic acid 1, ammediol ester random copolymers can be further derived from getting 1 of authigenic material, ammediol.
Term " biomass " is meant survival or dead biomaterial, and these materials can be directly or subsequently converted into common useful chemical substance derived from non-renewable hydrocarbons resource.Biomass can comprise the derivative of cellulose material, cereal, the starch derived from cereal, lipid acid, vegetables oil and these biomass examples.The example of useful chemical substance includes but not limited to glycol; Diacid; Be used to prepare the monomer of glycol or acid, for example Succinic Acid; Be used to monomer for preparing in polymkeric substance etc.Biomass based on glycol can obtain from several sources.For example, following method can be used to obtain based on 1 of biomass, the 4-butyleneglycol.The biomass of agriculture can change into Succinic Acid by simple method such as corn cereal or cereal deutero-sugar, such as the fermentation process in the presence of microorganism.This Succinic Acid can be bought from several sources commerce, such as the commodity " BioAmber of Diversified Natural Products Inc. company
TM".This Succinic Acid also can change into 1 by the method that is described in several pieces of open source literatures (as United States Patent (USP) 4,096,156), and the 4-butyleneglycol all is incorporated herein by reference this patent herein.1 of biomass derived, the 4-butyleneglycol also can change into tetrahydrofuran (THF), and further changes into polytetrahydrofuran, is also referred to as polyoxybutylene glycol (polybutylene oxide glycol).Described another kind among people's such as Smith the Life Cycles Engineering Guidelines Succinic Acid is changed into 1, the method for 4-butyleneglycol is described in the open EPA/600/R-1/101 (2001) of EPA.Based on 1 of biomass, ammediol also can obtain from commercial source, the method for the aerobic fermentation of adopting as DuPont, Tate and Lyle Bio Products.
But, preparation the application modification poly terephthalic acid 1, ammediol ester random copolymers is not limited to these polyethylene terephthalate components and 1, and ammediol carries out the method for depolymerization.In one embodiment, this modification poly terephthalic acid 1, ammediol ester random copolymers can prepare by the following method, it comprises: the polyethylene terephthalate component that (a) is selected from polyethylene terephthalate and pet copolymer by following depolymerization: under at least one atmospheric pressure, in the presence of catalyst component, and be enough to described polyethylene terephthalate component is depolymerized under the condition of first molten mixture, polyethylene terephthalate component and ethylene glycol are stirred in reactor, this first molten mixture contains the oligopolymer that is selected from the ethylene glycol terephthalate part, ethylene glycol, and the component of combination; (b) in the presence of catalyst component, in 190 ℃ to 240 ℃ temperature range, and be enough to form under the condition of second molten mixture, in first molten mixture of reactor, add 1, ammediol, this second molten mixture comprises and is selected from following component: contain the ethylene glycol terephthalate part oligopolymer, contain oligopolymer, the oligopolymer of blended glycol, propylene glycol, the ethylene glycol of propylene glycol ester terephthalate's part and combination thereof; (c) be lower than under the atmospheric condition in stirring and pressure, the temperature of second molten mixture is elevated to 240 ℃ to 260 ℃ temperature, thereby form poly terephthalic acid 1, ammediol ester random copolymers, this random copolymers (1) comprises at least a residue derived from the polyethylene terephthalate component derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer and (2).
The temperature that adopts in this method can change.For example, polyethylene terephthalate component temperature range that depolymerization can take place can be 190 ℃ to 250 ℃.These temperature may be used under the inert atmosphere.
In addition, the method of this PET component and ethylene glycol depolymerization can comprise a kind of embodiment, poly terephthalic acid 1 in this scheme, further derived from a kind of 1, ammediol, this alcohol are to be come by biomass derived by the method that comprises repeatedly transition process to ammediol ester random copolymers, biological example matter changes into starch, transform saccharogenesis again, change into 1 again, ammediol.This biomass can be cereals, for example corn, wheat and combination thereof.
Preparation modification poly terephthalic acid 1, the method for ammediol ester random copolymers can be carried out in the presence of catalyzer.This catalyzer can be selected from antimony compounds, tin compound, titanium compound and combination thereof, and the combination of disclosed many other metal catalysts and metal catalyst in the document.The amount of catalyzer will change according to concrete actual needs.The scope of appropriate catalyst amount is from 1 to 5000ppm, or more.
In use, this modification poly terephthalic acid 1, ammediol ester random copolymers can be used for making many goods with useful performance.
The application's modification poly terephthalic acid 1, ammediol ester random copolymers can pass through several different methods, different process is molded as useful goods, to provide the moulding product of usefulness, as injection moulding, extrude, rotational moulding, foaming, calendering formation and blowing and thermoforming, compression moulding, melt-spinning and melt and spray the goods of formation.Non-limitative example by the various goods of thermoplastic compounds of the present invention preparation comprises: fiber, such as fabric; Injection-molded item is such as junctor; Blow-molded article is such as fluid container.In one embodiment, this polyester can carry out blend with other conventional polymer.
Thus, the present invention includes poly terephthalic acid 1, the molding or the extruded product of ammediol ester random copolymers, this random copolymers (1) is derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer, (2) comprise at least a residue derived from the polyethylene terephthalate component, according to application, this residue can be any above-mentioned residue.Residue derived from the pet copolymer component, for example, can be selected from ethylene glycol group, diethylene glycol group, isophthalic acid group, 1,3-cyclohexane dimethanol, 1,3-cyclohexanedimethanol trans-isomer(ide), 1,4-cyclohexane dimethanol, 1,4 cyclohexane dimethanol trans-isomer(ide) and combination thereof.
Modification poly terephthalic acid 1, ammediol ester give goods useful performance.These performances can change, and depend on some factors, such as the performance performance of needs, the equipment that uses, processing parameter etc.In another embodiment, the limiting viscosity variation range is 1 to 1.3dL/g.In another embodiment, the limiting viscosity variation range is 0.95 to 1.05dL/g.All limiting viscosities all are meant the limiting viscosity of measuring at 25 ℃ among the application in the solution of the sym.-tetrachloroethane of the phenol of 60wt% and 40wt%.
This modification poly terephthalic acid 1, the fusing point of ammediol ester random copolymers are 200 ℃ at least or are 210 ℃ at least.In another embodiment, the variation of melting point scope is 220 to 230 ℃.In another embodiment, the variation of melting point scope is 210 to 225 ℃.This modification poly terephthalic acid 1, the Tc of ammediol ester random copolymers is at least 120 ℃.In another embodiment, the Tc variation range is 140 to 150 ℃.
This modification poly terephthalic acid 1, the tensile strength of ammediol ester random copolymers (@ fracture) are 30MPa at least.In another embodiment, the variation range of tensile strength is that 30MPa is to 100MPa.In another embodiment, the variation range of tensile strength is that 51MPa is to 565MPa.This modification poly terephthalic acid 1, the tensile elongation of ammediol ester random copolymers (@ surrender) is at least 2%.
In another embodiment, tensile elongation (fracture) variation range is 2% to 10%.In another embodiment, tensile elongation (@ fracture) variation range is 10 to 300%.This modification poly terephthalic acid 1, the notched izod impact strength of ammediol ester random copolymers (notchedizod strength) are 10J/m at least.In another embodiment, the notched izod impact strength variation range is that 20J/m is to 60J/m.In another embodiment, the notched izod impact strength variation range is that 20J/m is to 40J/m.
Other embodiment comprises the PTT of derived from PET and PET multipolymer and the mixture of other functional ingredient, these functional ingredient comprise filler, with alloy, impact modifier, fire retardant, stablizer, nucleator and the combination thereof of other polymkeric substance (such as polycarbonate).
The invention provides unprecedented advantage.For example, the invention provides from the effective ways of polyethylene terephthalate rather than monomer efficient production modified PTT random copolymers.In addition, the application's modified PTT random copolymers shows useful performance performance.In addition, can prepare goods, and then reduce the amount of being burned or pour into the polyethylene terephthalate of landfill usually from the application's modified PTT random copolymers.
For example, the method for preparing the random modified PTT multipolymer of PET deutero-also can reduce Carbon emission and carbonaceous wastes.Because the random modified PTT multipolymer of PET deutero-of method preparation of the present invention is by PET rather than monomer preparation, this method can reduce Carbon emission and carbonaceous wastes.In addition, biologically-derived 1 when using, during ammediol, further improved the influence of carbonic acid gas to the modified PTT multipolymer.
Following illustrative embodiment is described further to the present invention.Unless otherwise mentioned, wherein all umbers and per-cent is all by weight.
Embodiment 1
Green regenerating PET pellet (green colored recycle PET) obtains from North America supplier ST.Jude.The limiting viscosity that regenerative PET pellet after these human consumers use has (iv) specification is 0.68 to 0.78, and the fusing point specification is 245 to 255 ℃.1, ammediol (PDO) obtains from shell chemistry (ShellChemicals), its pureness specifications〉99.9wt%.Catalyzer TPT is the Tyzor from the industrial level of Du Pont (Dupont).
With 1 of 70.0 regenerative PET pellets that restrain and 84.04 grams, ammediol (mol ratio 1:3) mixes in the 500ml reactor.Oil bath temperature (being used for reactor) is elevated to 255 ℃ gradually from 180 ℃.Stirring velocity is set to 20rpm.In this stage, the TPT catalyzer of 0.08ml also is added in the reaction mixture.Reactant arrives 214 ℃ (1, the boiling point of ammediol), and PDO refluxed 2 hours under this temperature.This is known as the glycolysis stage of PET.
For polymerization stage, reflux exchanger is removed, reactor is vacuumized.Two excessive pure and mild other volatility partly are collected in " Dean-Rodney Stark (Dean and Stark) " condenser.Stirring velocity is increased to 220rpm.Use vacuum pump to reduce pressure, reach 0.15torr until pressure with the speed of 40torr/min.The increase of polymericular weight is to monitor by the increase of the moment of torsion of overhead, reaches after the maximum torque of agitator, and stir speed (S.S.) reduces, and reaction is carried out.220,120, after 60rpm reaches three successive maximum torque, this polymerization stage is finished.Collecting about 10 gram polyester from reactor further tests and analyzes.Polyester sample is carried out following test: limiting viscosity (IV), nuclear-magnetism (NMR) are analyzed and differential calorimetric scanning (DSC) is analyzed.The component of this material of NMR analysis revealed of resin comprises the poly terephthalic acid 1 of 98.3mol%, the PET residue of ammediol ester and 1.63mol%.This properties of materials viscosity is 0.736dL/g.(temperature rise rate is 20 ℃/min) measurement, is respectively 222 ℃ and 144 ℃ by DSC for fusing point and Tc.The Heat of fusion of these transformations and heat of crystallization be respectively 36 and-37J/g.
Although be described in detail with reference to preferred versions more of the present invention, other change is possible.Therefore, the spirit and scope of claims should not be subject to the description of the scheme that this paper comprises.
Claims (27)
1. composition, it comprises poly terephthalic acid 1, ammediol ester random copolymers, this random copolymers (1) comprises at least a residue derived from described polyethylene terephthalate component derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer and (2).
2. the described composition of claim 1, wherein the residue derived from the polyethylene terephthalate component is selected from the ethylene glycol group, diethylene glycol group, isophthalic acid group, antimony containing compounds, germanium-containing compound, titanium-containing compound, cobalt compound, sn-containing compound, 1,3-cyclohexanedimethanol isomer, 1,4-cyclohexanedimethanol isomer, 1, the 3-cyclohexane dimethanol, 1, the 4-cyclohexane dimethanol, 1,3-cyclohexanedimethanol trans-isomer(ide), 1,4-cyclohexanedimethanol trans-isomer(ide), P contained compound and negatively charged ion, sulfocompound and negatively charged ion, naphthalene dicarboxylic acids, 1, ammediol group, and combination.
3. the described composition of claim 1, wherein at least a residue derived from the polyethylene terephthalate component comprises the mixture of ethylene glycol and glycol ether.
4. the described composition of claim 3, wherein the residue derived from the polyethylene terephthalate component further comprises m-phthalic acid.
5. the described composition of claim 3, wherein the residue derived from the polyethylene terephthalate component further comprises 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, 1,3-cyclohexanedimethanol trans-isomer(ide), 1,4 cyclohexane dimethanol trans-isomer(ide) and combination thereof.
6. the described composition of claim 1, wherein the residue derived from the polyethylene terephthalate component is selected from 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, 1,3-cyclohexanedimethanol trans-isomer(ide), 1,4 cyclohexane dimethanol trans-isomer(ide) and combination thereof.
7. the described composition of claim 1, wherein the residue derived from the polyethylene terephthalate component is selected from ethylene glycol group, diethylene glycol group, isophthalic acid group, 1,3-cyclohexane dimethanol, 1,3-cyclohexanedimethanol trans-isomer(ide), 1,4-cyclohexane dimethanol, 1,4 cyclohexane dimethanol trans-isomer(ide) and combination thereof.
8. the described composition of claim 1, wherein at least a residue derived from the polyethylene terephthalate component comprises the mixture of following material: ethylene glycol, glycol ether and cobalt compound, antimony containing compounds, sn-containing compound, germanium-containing compound and combination thereof.
9. the described composition of claim 8, wherein at least a residue derived from the polyethylene terephthalate component further comprises isophthalic acid group.
10. the described composition of claim 1, wherein the residue derived from the polyethylene terephthalate component is selected from ethylene glycol group, diethylene glycol group and cyclohexanedimethanol group, and the amount of this residue is 0.1 to 10mol%, is as the criterion in the glycol of 100mol% in the composition.
11. the described composition of claim 10, wherein the residue derived from the polyethylene terephthalate component further comprises isophthalic acid group, its content is 0 to 10mol%, with this poly terephthalic acid 1, and the acid functional group of the 100mol% meter that is as the criterion in the ammediol ester copolymer.
A 12. composition molding according to claim 1 or extrude the goods of making.
A 13. composition molding according to claim 7 or extrude the goods of making.
14. the described composition of claim 1, wherein poly terephthalic acid 1, ammediol ester random copolymers further derived from obtain by biomass 1, ammediol.
15. the described composition of claim 14, wherein biomass are cereals.
16. the described composition of claim 15, wherein cereal is selected from corn, wheat and combination thereof.
17. one kind prepares the described method for compositions of claim 1, it comprises:
(a) be selected from the polyethylene terephthalate component of polyethylene terephthalate and pet copolymer by following depolymerization: with (i) polyethylene terephthalate component and (ii) 1, ammediol is under at least one atmospheric pressure, in the presence of catalyst component, and be enough to described polyethylene terephthalate component depolymerized under the inert atmosphere conditions of molten mixture and react, this molten mixture comprises the oligopolymer of poly terephthalic acid ethylene glycol, poly terephthalic acid 1, the oligopolymer of ammediol ester, the oligopolymer of blended glycol, 1, ammediol and ethylene glycol;
Wherein, in step (a) process, described polyethylene terephthalate component and 1, ammediol mixes in liquid phase, with 1, ammediol backflow Returning reactor;
(b) molten mixture is placed be lower than under the atmospheric environment, and the temperature of this molten mixture that raises, until being enough to form poly terephthalic acid 1, the temperature of ammediol ester random copolymers, this random copolymers (1) comprises at least a residue derived from described polyethylene terephthalate component derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer and (2).
18. the described method of claim 16, wherein the polyethylene terephthalate component is 180 ℃ to 260 ℃ temperature range generation depolymerization.
19. the described method of claim 16, wherein the temperature of molten mixture is elevated to 240 ℃ to 270 ℃ temperature.
20. the described method of claim 16, wherein poly terephthalic acid 1, ammediol ester random copolymers further derived from obtain by biomass 1, ammediol.
21. the described method of claim 20, wherein biomass are cereals.
22. the described method of claim 21, wherein cereal is selected from corn, wheat and combination thereof.
23. one kind prepares the described method for compositions of claim 1, it comprises:
Be selected from the polyethylene terephthalate component of polyethylene terephthalate and pet copolymer by following depolymerization: under at least one atmospheric pressure, in the presence of catalyst component, and be enough to described polyethylene terephthalate component is depolymerized under the condition of first molten mixture, in reactor, stir polyethylene terephthalate component and ethylene glycol, this first molten mixture contains oligopolymer, the ethylene glycol that is selected from the ethylene glycol terephthalate part, and combination;
In the presence of catalyst component, in 190 ℃ to 240 ℃ temperature range, and be enough to form under the condition of second molten mixture, in first molten mixture of reactor, add 1, ammediol, this second molten mixture comprises and is selected from following component: contain the ethylene glycol terephthalate part oligopolymer, contain oligopolymer, blended oligomers of glycols, propylene glycol, the ethylene glycol of propylene glycol ester terephthalate's part and combination thereof; With
(c) be lower than under the atmospheric condition in stirring and pressure, the temperature of second molten mixture is elevated to 240 ℃ to 260 ℃ temperature, thereby form poly terephthalic acid 1, ammediol ester random copolymers, this random copolymers (1) comprises at least a residue derived from the polyethylene terephthalate component derived from the polyethylene terephthalate component that is selected from polyethylene terephthalate and pet copolymer and (2).
24. the described method of claim 23, wherein depolymerization takes place in the polyethylene terephthalate component under inert atmosphere in 190 ℃ to 250 ℃ temperature ranges.
25. the described method of claim 24, wherein poly terephthalic acid 1, ammediol ester random copolymers further derived from obtain by biomass 1, ammediol.
26. the described method of claim 24, wherein biomass are cereals.
27. the described method of claim 26, wherein cereal is selected from corn, wheat and combination thereof.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76309306P | 2006-01-27 | 2006-01-27 | |
| US60/763,093 | 2006-01-27 | ||
| US60/777,901 | 2006-03-01 | ||
| US60/820,447 | 2006-07-26 | ||
| US11/616,373 | 2006-12-27 |
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| Publication Number | Publication Date |
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| CN101395211A true CN101395211A (en) | 2009-03-25 |
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| CNA2007800081651A Pending CN101395211A (en) | 2006-01-27 | 2007-01-26 | Process for making polybutylene terephthalate (pbt) from polyethylene terephthalate (pet) |
| CNA2007800104136A Pending CN101415746A (en) | 2006-01-27 | 2007-01-26 | Process for making polybutylene terephthalate (PBT) from polyethylene terephthalate (PET) |
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| CNA2007800104136A Pending CN101415746A (en) | 2006-01-27 | 2007-01-26 | Process for making polybutylene terephthalate (PBT) from polyethylene terephthalate (PET) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107580616A (en) * | 2015-04-30 | 2018-01-12 | 三星电子株式会社 | The method of polymer composition, moulding article and the manufacture moulding article |
| CN111349219A (en) * | 2019-12-20 | 2020-06-30 | 张家港美景荣化学工业有限公司 | Preparation method of PET (polyethylene terephthalate) modified PTT (polytrimethylene terephthalate) |
| CN114986741A (en) * | 2022-06-22 | 2022-09-02 | 惠州市艾宝特智能科技股份有限公司 | Production method of PET bottle embryo and bottle embryo prepared by same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731760B (en) * | 2012-07-17 | 2014-03-26 | 龙福环能科技股份有限公司 | Method for carrying out alcoholysis and then polymerization on recycled polyester bottle chip melts |
| CN110333315A (en) * | 2019-06-11 | 2019-10-15 | 中塑联新材料科技湖北有限公司 | Low energy consumption is pollution-free complete utilization terylene waste spinning electronation PBT testing production line |
| EP4048727A1 (en) * | 2019-10-25 | 2022-08-31 | Eastman Chemical Company | Crystallizable shrinkable films and thermoformable films and sheets made from reactor grade resins with recycled content |
| CN111040144A (en) * | 2019-12-31 | 2020-04-21 | 树业环保科技股份有限公司 | PBT preparation method based on clean production |
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2007
- 2007-01-26 CN CNA2007800081651A patent/CN101395211A/en active Pending
- 2007-01-26 CN CNA2007800104136A patent/CN101415746A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107580616A (en) * | 2015-04-30 | 2018-01-12 | 三星电子株式会社 | The method of polymer composition, moulding article and the manufacture moulding article |
| CN111349219A (en) * | 2019-12-20 | 2020-06-30 | 张家港美景荣化学工业有限公司 | Preparation method of PET (polyethylene terephthalate) modified PTT (polytrimethylene terephthalate) |
| CN114986741A (en) * | 2022-06-22 | 2022-09-02 | 惠州市艾宝特智能科技股份有限公司 | Production method of PET bottle embryo and bottle embryo prepared by same |
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| CN101415746A (en) | 2009-04-22 |
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